US9267095B2 - Low pH detergent composition comprising nonionic surfactants - Google Patents

Low pH detergent composition comprising nonionic surfactants Download PDF

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US9267095B2
US9267095B2 US14/284,418 US201414284418A US9267095B2 US 9267095 B2 US9267095 B2 US 9267095B2 US 201414284418 A US201414284418 A US 201414284418A US 9267095 B2 US9267095 B2 US 9267095B2
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acid
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US20140349908A1 (en
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Sarah Ann DELANEY
Eugene Steven Sadlowski
Cheyne THOMAS
Peggy Marion Teyssier
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Procter and Gamble Co
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    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66Non-ionic compounds
    • C11D1/825Mixtures of compounds all of which are non-ionic
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66Non-ionic compounds
    • C11D1/83Mixtures of non-ionic with anionic compounds
    • C11D1/8305Mixtures of non-ionic with anionic compounds containing a combination of non-ionic compounds differently alcoxylised or with different alkylated chains
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/20Organic compounds containing oxygen
    • C11D3/2075Carboxylic acids-salts thereof
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66Non-ionic compounds
    • C11D1/72Ethers of polyoxyalkylene glycols

Definitions

  • the present disclosure relates generally to detergent compositions and, more specifically, to low pH detergent compositions comprising nonionic surfactants that are suitable for washing of clothes, and methods of making and using the same.
  • compositions with viscosities that are too high may be difficult to process or to use; viscosities that are too low may indicate a lack of cleaning power or value to the consumer.
  • many detergents especially those that have high levels of water (e.g., above 60%), require the use of thickening agents.
  • a formulator may add salt, such as sodium chloride or sodium formate, to thicken compositions that have low viscosities.
  • thickening agents can present difficulties.
  • certain thickening agents such as salt, may have corrosive effects at low pH on metals commonly used in manufacturing plants, such as 316 stainless steel.
  • Thickening agents may lead to stability challenges such as “salting out.” There may be limits to the amount of viscosity that can be built with thickening agents. And, of course, the use of thickening agents adds extra cost to a composition.
  • a liquid laundry detergent composition comprising: from about 2% to about 20% by weight of the composition of a surfactant system, where the surfactant system comprises a first nonionic surfactant (A) where A has an HLB less than about 10, a second nonionic surfactant (B) where B has an HLB greater than about 10, where the weight ratio of A:B is from about 1:100 to about 40:100, and anionic surfactant; where the composition has a neat pH of from about 1.5 to about 6.9; and where the composition has a viscosity of from about 200 cps to about 3000 measured at 20 s ⁇ 1 at 21.1° C.
  • A nonionic surfactant
  • B second nonionic surfactant
  • anionic surfactant where the composition has a neat pH of from about 1.5 to about 6.9
  • the composition has a viscosity of from about 200 cps to about 3000 measured at 20 s ⁇ 1 at 21.1° C.
  • the present disclosure also provides a liquid laundry detergent composition
  • a liquid laundry detergent composition comprising: from about 2% to about 20% by weight of the composition of a surfactant system, where the surfactant system comprises a first nonionic surfactant (A) where A has an HLB less than about 10, a second nonionic surfactant (B) where B has an HLB greater than about 10, where the weight ratio of A:B is from about 1:100 to about 40:100, and anionic surfactant; from about 5% to about 15% by weight of the composition of organic acid, where the organic acid comprises 6 carbon atoms or fewer; from about 60% to about 90% water; where the composition has a neat pH of from about 2 to about 4; and where the composition has a viscosity of from about 200 cps to about 1200 cps measured at 20 s ⁇ 1 at 21.1° C.
  • the present disclosure provides a method for treating a surface comprising the step of contacting the surface with the compositions described herein.
  • compositions of the present invention can comprise, consist essentially of, or consist of, the components of the present disclosure.
  • the terms “substantially free of” or “substantially free from” may be used herein. This means that the indicated material is at the very minimum not deliberately added to the composition to form part of it, or, preferably, is not present at analytically detectable levels. It is meant to include compositions whereby the indicated material is present only as an impurity in one of the other materials deliberately included.
  • component or composition levels are in reference to the active portion of that component or composition, and are exclusive of impurities, for example, residual solvents or by-products, which may be present in commercially available sources of such components or compositions.
  • compositions disclosed herein are low pH liquid laundry detergent compositions comprising nonionic surfactants.
  • the compositions typically comprise a mixture of nonionic surfactants. It is believed that a mixture of high HLB (hydrophilic-lipophilic balance) nonionic surfactant and low HLB nonionic surfactant builds viscosity through the creation of micelles. Micelles are the structural arrangements resulting from hydrophobic tails of the surfactants arranging to avoid contact with water, thereby minimizing the area to volume ratio, and from hydrophilic head groups repelling from each other, thereby maximizing the area to volume ratio.
  • nonionic mixtures of the present compositions lead to the creation of worm-like micelles, as evidenced by a drop in viscosity at high shear and by shear induced birefringence. Because viscosity is built through the selection of surfactants, in some aspects, the compositions described herein do not require the addition of thickening agents, such as salt.
  • the detergent compositions of the present invention may be in liquid, gel, or paste form.
  • the compositions are typically liquids.
  • the compositions comprise from about 50% to about 95%, or from about 60% to about 90%, or from about 65% to about 81%, by weight of the composition, water.
  • the compositions may comprise at least 50%, or at least 60%, or at least 70%, or at least 75%, or at least 80%, or at least 85% water.
  • the composition is in a unit dose form, where the composition is encapsulated in a water-soluble film or pouch; the water-soluble film or pouch may comprise polyvinyl alcohol, polyvinyl acetate, or mixtures thereof.
  • the unit dose form comprises at least two compartments, or at least three compartments. In some aspects, at least one compartment may be superimposed on another compartment.
  • compositions may be isotropic at 22° C.
  • isotropic means a clear mixture having a % transmittance of greater than 50% at a wavelength of 570 nm measured via a standard 10 mm pathlength cuvette with a Beckman DU spectrophotometer, in the absence of dyes and/or opacifiers.
  • liquid cleaning compositions herein as well as preparation and use, are described in greater detail as follows.
  • the detergent compositions described herein comprise from about 2% to about 20%, or from about 9% to about 20%, or from about 5% to about 15%, or from about 7% to about 12% by weight of the detergent composition of a surfactant system.
  • the surfactant system may comprise a detersive surfactant selected from nonionic surfactants, anionic surfactants, amphoteric surfactants, zwitterionic surfactants, cationic surfactants, or mixtures thereof.
  • the surfactant system comprises nonionic surfactant, anionic surfactant, or mixtures thereof.
  • the surfactant system consists of a nonionic surfactant and an anionic surfactant, e.g., a blend of two nonionic surfactants and an anionic surfactant.
  • the composition may be substantially free of zwitterionic surfactant.
  • a detersive surfactant encompasses any surfactant or mixture of surfactants that provide cleaning, stain removing or other laundering benefit to fabrics during the laundering process.
  • the surfactant system of the present compositions comprises a nonionic surfactant.
  • the surfactant system may comprise a first nonionic surfactant (A) and a second nonionic surfactant (B).
  • the surfactant system comprises no more than two nonionic surfactants.
  • the weight ratio of the first nonionic surfactant to the second nonionic surfactant (A:B) may be from about 1:100 to about 40:100, or from about 10:100 to about 30:100, or from about 15:100 to about 25:100.
  • the detergent composition comprises from about 1% to about 12%, or from about 2% to about 10%, or from about 4% to about 8%, by weight of the detergent composition, of nonionic surfactant.
  • Suitable nonionic surfactants useful herein include any of the conventional nonionic surfactants typically used in detergent products. These include, for example, alkoxylated fatty alcohols and amine oxide surfactants. Generally, the nonionic surfactants used herein are liquids.
  • the nonionic surfactant may be an ethoxylated nonionic surfactant. These materials are described in U.S. Pat. No. 4,285,841, Barrat et al, issued Aug. 25, 1981.
  • the nonionic surfactant is selected from the ethoxylated alcohols and ethoxylated alkyl phenols of the formula R(OC 2 H 4 ) n OH, where R is selected from the group consisting of aliphatic hydrocarbon radicals containing from about 8 to about 18 carbon atoms and alkyl phenyl radicals in which the alkyl groups contain from about 8 to about 12 carbon atoms, and the average value of n is from about 5 to about 15.
  • R is selected from the group consisting of aliphatic hydrocarbon radicals containing from about 8 to about 18 carbon atoms and alkyl phenyl radicals in which the alkyl groups contain from about 8 to about 12 carbon atoms, and the average value of n is from about 5 to about 15.
  • the nonionic surfactant is selected from ethoxylated alcohols (also known as fatty alcohol ethoxylates) having an average of from about 10 to about 16 carbon atoms in the alcohol and an average degree of ethoxylation of from about 1 to about 12 moles of ethylene oxide per mole of alcohol.
  • ethoxylated alcohols also known as fatty alcohol ethoxylates
  • a shorthand method of naming a fatty alcohol ethoxylate refers to its number of carbons in the alkyl chain and its average number of ethoxylate (EO) groups.
  • EO ethoxylate
  • a fatty alcohol ethoxylate with from twelve to fourteen carbon atoms in its alkyl chain and an average of nine ethoxylate groups can be written as “C12,14 EO9”. This naming convention is used in this application.
  • the nonionic surfactant comprises C12-C18 alkyl ethoxylate.
  • the C12-C18 alkyl ethoxylate is selected from the group consisting of: C12,14 EO9; C12,14 EO7; C12,15 EO3; and mixtures thereof.
  • the C12-C18 alkyl ethoxylate is C12,14 EO7 and C12,15 EO3, and in some aspects, the molar ratio of C12,14 EO7 to C12,15 EO3 is about 2:1.
  • Amine oxides are materials which are often referred to in the art as “semi-polar” nonionics. Amine oxides may have the formula: R(EO) x (PO) y (BO) z N(O)(CH 2 R′) 2 .qH 2 O.
  • R is a relatively long-chain hydrocarbyl moiety which can be saturated or unsaturated, linear or branched, and can contain from 8 to 20, in one embodiment from 10 to 16 carbon atoms, and is alternatively a C 12 -C 16 primary alkyl.
  • R′ is a short-chain moiety, and may be selected from hydrogen, methyl and —CH 2 OH.
  • EO ethyleneoxy
  • PO propyleneneoxy
  • BO butyleneoxy
  • Amine oxide surfactants are non-limitingly illustrated by C 12-14 alkyldimethyl amine oxide. In some aspects, the surfactant system is substantially free of semi-polar nonionic surfactants, or of amine oxides.
  • nonionic surfactants useful herein include: a) C 12 -C 18 alkyl ethoxylates, such as, NEODOL® nonionic surfactants from Shell; b) C 6 -C 12 alkyl phenol alkoxylates where the alkoxylate units are a mixture of ethyleneoxy and propyleneoxy units; c) C 12 -C 18 alcohol and C 6 -C 12 alkyl phenol condensates with ethylene oxide/propylene oxide block polymers such as Pluronic® from BASF; d) Alkylpolysaccharides as discussed in U.S. Pat. No. 4,565,647 to Llenado, issued Jan.
  • Nonionic surfactants can be classified by the balance between the hydrophilic and lipophilic moieties in the surfactant molecule.
  • the hydrophile-lipophile balance (HLB) scale devised by Griffin in 1949 is a scale from 0-20 (20 being Hydrophilic) used to characterise the nature of surfactants.
  • HLB value of 0 corresponds to a completely lipophilic/hydrophobic molecule
  • a value of 20 corresponds to a completely hydrophilic/lipophobic molecule.
  • the HLB values for commonly-used surfactants are readily available in the literature (e.g., HLB Index in McCutcheon's Emulsifiers and Detergents, MC Publishing Co., 2004).
  • the HLB value for a mixture of surfactants can be calculated as a weighted average of the HLB values of the surfactants.
  • a typical nonionic alcohol ethoxylate surfactant has the following formula: H 3 C—(CH 2 ) m —(O—CH 2 —CH 2 ) n —OH
  • the (H 3 C—(CH 2 ) m ) portion of the formula is the hydrophobic portion, and the ((O—CH 2 —CH 2 ) n —OH) portion is the hydrophilic portion.
  • the molar mass of the hydrophilic portion (Mh) can be calculated by n*44+17, where n is the number of ethoxylate groups (EO).
  • Table 1 shows a non-limiting list of exemplary nonionic surfactants and their corresponding HLB values.
  • the HLB value is calculated using the equation referenced above.
  • Commercially available nonionic surfactants typically consist of a distribution of alcohol chain lengths. In order to estimate the molar mass, an average chain length is used, unless otherwise specified in the material specifications.
  • the alkoxylated fatty alcohol materials useful in the detergent compositions herein typically have HLB values that range from about 3 to about 17, or from about 6 to about 15, or from about 8 to about 15.
  • the first nonionic surfactant (A) has a HLB value less than about 10, or less than about 9.5, or less than about 9, or less than about 8.5, or less than about 8.
  • the first nonionic surfactant (A) is a fatty alcohol ethoxylate selected from the group consisting of: C12,13 EO1; C12,13 EO1.5; C12,13 EO2; C12,13 EO3; and mixtures thereof.
  • the first nonionic surfactant (A) is selected from the group consisting of: C12,13 EO2; C12,13 EO3; and mixtures thereof.
  • the second nonionic surfactant (B) has a HLB value greater than about 10, or greater than about 10.5, or greater than about 11, or greater than about 11.5, or greater than about 12.
  • the second nonionic surfactant (B) is a fatty alcohol ethoxylate selected from the group consisting of: C9,11 EO5; C11,16 EO7; C12,13 EO5; C12,13 EO6.5; C12,13 EO8; C12,13 EO9; C12,14 EO7; C12,14 EO8; C12,14 EO9; C14,15 EO5; C14,15 EO7; C14,15 EO8; C11 EO9; C12,14 EO9; C12,15 EO7; C12,15 EO10; C14,15 EO8; C14,15 EO9; C14,18 EO9; C10 EO3; C10 EO6; C12 EO3; C12 EO6; C12 EO3
  • the detergent composition has a ⁇ HLB, calculated as the difference between the HLB of the second nonionic surfactant (B) and the HLB of the first nonionic surfactant (A).
  • the composition has a ⁇ HLB of at least about 1, or at least about 2, or at least about 3, or at least about 4, or at least about 5.
  • the composition has a ⁇ HLB of from about 1 to about 10, or from about 1.5 to about 6, or from about 2 to about 5, or from about 2 to about 3.5.
  • the HLB of the mixture of the first and the second nonionic surfactants is from about 8 to about 10, or is about 9. In some aspects, the HLB of the surfactant system of the detergent composition is from about 8 to about 10, or is about 9.
  • the surfactant system typically comprises anionic surfactant.
  • the composition comprises, by weight of the detergent composition, from about 1% to about 25%, or from about 2% to about 20%, or from about 5% to about 15%, of anionic surfactant.
  • Suitable anionic surfactants include any conventional anionic surfactant used in detergent products. These include, for example, the alkyl benzene sulfonic acids and their salts as well as alkoxylated or non-alkoxylated alkyl sulfate materials.
  • the anionic surfactants may be present in acid form or in neutralized (e.g., salt) form.
  • the anionic surfactants may be linear, branched, or a mixture thereof.
  • Exemplary anionic surfactants are the alkali metal salts of C 10 -C 18 alkyl benzene sulfonic acids or C 11 -C 14 alkyl benzene sulfonic acids.
  • the alkyl group is linear, and such linear alkyl benzene sulfonates are known as “LAS.”
  • Alkyl benzene sulfonates, and particularly LAS, are well known in the art.
  • Such surfactants and their preparation are described in, for example, U.S. Pat. Nos. 2,220,099 and 2,477,383.
  • sodium and potassium linear straight chain alkylbenzene sulfonates in which the average number of carbon atoms in the alkyl group is from about 11 to about 14.
  • Sodium C 11 -C 14 e.g., C 12
  • LAS is a specific example of such surfactants.
  • alkoxylated alkyl sulfate surfactants Preferred are ethoxylated alkyl sulfate surfactants.
  • ethoxylated alkyl sulfate surfactants Such materials are also known as alkyl ether sulfates, alkyl polyethoxylate sulfates, or simply “AES,” and correspond to the formula: R′—O—(C 2 H 4 O) n SO 3 M, where R′ is a C 8 -C 20 alkyl group; n is from about 0.5 to about 20, or from about 1 to about 20; and M is a salt-forming cation.
  • R′ is a C 10 -C 18 alkyl; n is from about 1 to about 15; and M is sodium, potassium, ammonium, alkylammonium, or alkanolammonium. In one aspect, R′ is a C 12 -C 16 alkyl; n is from about 0.5 to about 6, or from about 1 to about 6; and M is sodium.
  • AS non-ethoxylated alkyl sulfate
  • Non-ethoxylated alkyl sulfates may also be added separately to the compositions of the invention.
  • Specific examples of non-alkoxylated alkyl ether sulfate surfactants are those produced by the sulfation of higher C 8 -C 20 fatty alcohols.
  • Conventional primary alkyl sulfate surfactants have the general formula: ROSO 3 -M + where R is a linear C 8 -C 20 hydrocarbyl group and M is a water-solubilizing cation.
  • R is a C 10 -C 15 alkyl and M is alkali metal, more specifically R is C 12 -C 14 and M is sodium.
  • the surfactants of the present compositions may be branched detersive surfactants.
  • Suitable branched detersive surfactants include anionic branched surfactants selected from branched sulphate or branched sulphonate surfactants, e.g., branched alkyl sulphate, branched alkyl alkoxylated sulphate, and branched alkyl benzene sulphonates, comprising one or more random alkyl branches, e.g., C 1-4 alkyl groups, typically methyl and/or ethyl groups.
  • the branched detersive surfactant is a mid-chain branched detersive surfactant, typically, a mid-chain branched anionic detersive surfactant, for example, a mid-chain branched alkyl sulphate and/or a mid-chain branched alkyl benzene sulphonate.
  • the detersive surfactant is a mid-chain branched alkyl sulphate.
  • the mid-chain branches are C 1-4 alkyl groups, typically methyl and/or ethyl groups.
  • the branched surfactant comprises a longer alkyl chain, mid-chain branched surfactant compound of the formula: A b -X—B where:
  • a b is a hydrophobic C9 to C22 (total carbons in the moiety), typically from about C12 to about C18, mid-chain branched alkyl moiety having: (1) a longest linear carbon chain attached to the —X—B moiety in the range of from 8 to 21 carbon atoms; (2) one or more C1-C3 alkyl moieties branching from this longest linear carbon chain; (3) at least one of the branching alkyl moieties is attached directly to a carbon of the longest linear carbon chain at a position within the range of position 2 carbon (counting from carbon #1 which is attached to the —X—B moiety) to position ⁇ 2 carbon (the terminal carbon minus 2 carbons, i.e., the third carbon from the end of the longest linear carbon chain); and (4) the surfactant composition has an average total number of carbon atoms in the A b -X moiety in the above formula within the range of greater than 14.5 to about 17.5 (typically from about 15 to about 17);
  • B is a hydrophilic moiety selected from sulfates, sulfonates, amine oxides, polyoxyalkylene (such as polyoxyethylene and polyoxypropylene), alkoxylated sulfates, polyhydroxy moieties, phosphate esters, glycerol sulfonates, polygluconates, polyphosphate esters, phosphonates, sulfosuccinates, sulfosuccaminates, polyalkoxylated carboxylates, glucamides, taurinates, sarcosinates, glycinates, isethionates, dialkanolamides, monoalkanolamides, monoalkanolamide sulfates, diglycolamides, diglycolamide sulfates, glycerol esters, glycerol ester sulfates, glycerol ethers, glycerol ether sulfates, polyglycerol
  • X is selected from —CH2- and —C(O)—.
  • the A b moiety does not have any quaternary substituted carbon atoms (i.e., 4 carbon atoms directly attached to one carbon atom).
  • the resultant surfactant may be anionic, nonionic, cationic, zwitterionic, amphoteric, or ampholytic.
  • B is sulfate and the resultant surfactant is anionic.
  • the branched surfactant comprises a longer alkyl chain, mid-chain branched surfactant compound of the above formula wherein the A b moiety is a branched primary alkyl moiety having the formula:
  • R, R1, and R2 are each independently selected from hydrogen and C1-C3 alkyl (typically methyl), provided R, R1, and R2 are not all hydrogen and, when z is 0, at least R or R1 is not hydrogen; w is an integer from 0 to 13; x is an integer from 0 to 13; y is an integer from 0 to 13; z is an integer from 0 to 13; and w+x+y+z is from 7 to 13.
  • the branched surfactant comprises a longer alkyl chain, mid-chain branched surfactant compound of the above formula wherein the A b moiety is a branched primary alkyl moiety having the formula selected from:
  • mid-chain branched surfactant compounds described above, certain points of branching (e.g., the location along the chain of the R, R 1 , and/or R 2 moieties in the above formula) are preferred over other points of branching along the backbone of the surfactant.
  • the formula below illustrates the mid-chain branching range (i.e., where points of branching occur), preferred mid-chain branching range, and more preferred mid-chain branching range for mono-methyl branched alkyl A b moieties.
  • the branched anionic surfactant comprises a branched modified alkylbenzene sulfonate (MLAS), as discussed in WO 99/05243, WO 99/05242, WO 99/05244, WO 99/05082, WO 99/05084, WO 99/05241, WO 99/07656, WO 00/23549, and WO 00/23548.
  • MLAS branched modified alkylbenzene sulfonate
  • the branched anionic surfactant comprises a C12/13 alcohol-based surfactant comprising a methyl branch randomly distributed along the hydrophobe chain, e.g., Safol®, Marlipal® available from Sasol.
  • branched anionic detersive surfactants include surfactants derived from alcohols branched in the 2-alkyl position, such as those sold under the trade names Isalchem®123, Isalchem®125, Isalchem®145, Isalchem®167, which are derived from the oxo process. Due to the oxo process, the branching is situated in the 2-alkyl position.
  • These 2-alkyl branched alcohols are typically in the range of C11 to C14/C15 in length and comprise structural isomers that are all branched in the 2-alkyl position. These branched alcohols and surfactants are described in US20110033413.
  • Suitable branched surfactants include those disclosed in U.S. Pat. No. 6,037,313 (P&G), WO9521233 (P&G), U.S. Pat. No. 3,480,556 (Atlantic Richfield), U.S. Pat. No. 6,683,224 (Cognis), US20030225304A1 (Kao), US2004236158A1 (R&H), U.S. Pat. No. 6,818,700 (Atofina), US2004154640 (Smith et al), EP1280746 (Shell), EP1025839 (L'Oreal), U.S. Pat. No. 6,765,119 (BASF), EP108084 (Dow), U.S. Pat. No.
  • branched anionic detersive surfactants include surfactant derivatives of isoprenoid-based polybranched detergent alcohols, as described in US 2010/0137649. Isoprenoid-based surfactants and isoprenoid derivatives are also described in the book entitled “Comprehensive Natural Products Chemistry: Isoprenoids Including Carotenoids and Steroids (Vol. two)”, Barton and Nakanishi, ⁇ 1999, Elsevier Science Ltd and are included in the structure E, and are hereby incorporated by reference.
  • branched anionic detersive surfactants include those derived from anteiso- and iso-alcohols. Such surfactants are disclosed in WO2012009525.
  • branched anionic detersive surfactants include those described in US Patent Application Nos. 2011/0171155A1 and 2011/0166370A1.
  • Suitable branched anionic surfactants also include Guerbet-alcohol-based surfactants.
  • Guerbet alcohols are branched, primary monofunctional alcohols that have two linear carbon chains with the branch point always at the second carbon position. Guerbet alcohols are chemically described as 2-alkyl-1-alkanols. Guerbet alcohols generally have from 12 carbon atoms to 36 carbon atoms.
  • the Guerbet alcohols may be represented by the following formula: (R1)(R2)CHCH 2 OH, where R1 is a linear alkyl group, R2 is a linear alkyl group, the sum of the carbon atoms in R1 and R2 is 10 to 34, and both R1 and R2 are present. Guerbet alcohols are commercially available from Sasol as Isofol® alcohols and from Cognis as Guerbetol.
  • the surfactant system disclosed herein may comprise any of the branched surfactants described above individually or the surfactant system may comprise a mixture of the branched surfactants described above. Furthermore, each of the branched surfactants described above may include a bio-based content. In some aspects, the branched surfactant has a bio-based content of at least about 50%, at least about 60%, at least about 70%, at least about 80%, at least about 90%, at least about 95%, at least about 97%, or about 100%.
  • the surfactant system may comprise a mixture of anionic surfactant and nonionic surfactant, e.g., linear alkyl benzene sulfonic acid and C12-18 alkyl ethoxylate.
  • the weight ratio of anionic surfactant to nonionic surfactant is from about 1:100 to about 5:1, or from about 1:100 to about 3:1, or from about 1:100 to about 1:1, or from about 40:100 to about 75:100.
  • the detergent compositions of the present invention may comprise an organic acid.
  • the organic acid may be in the form of an organic carboxylic acid or polycarboxylic acid.
  • organic acids that may be used include: acetic acid, adipic acid, aspartic acid, carboxymethyloxymalonic acid, carboxymethyloxysuccinic acid, citric acid, formic acid, glutaric acid, hydroxyethyliminodiacetic acid, iminodiacetic acid, lactic acid, maleic acid, malic acid, malonic acid, oxydiacetic acid, oxydisuccinic acid, succinic acid, sulfamic acid, tartaric acid, tartaric-disuccinic acid, tartaric-monosuccinic acid, or mixtures thereof.
  • the organic acid is selected from the group consisting of lactic acid, acetic acid, citric acid, and mixtures thereof. In some aspects, the organic acid is citric acid. In some aspects, the composition comprises organic acids that can also serve as detergent builders, such as citric acid.
  • the organic acid may be a water-soluble or water-miscible acid.
  • the organic acid has a solubility in water at 20° C. of at least about 10 g acid/100 ml water, or at least about 30 g acid/100 ml water, or at least about 50 g acid/100 ml water, or at least about 70 g acid/100 ml water, or at least about 85 g/100 ml water.
  • the composition is substantially free of fatty acid.
  • the organic acid may be a low-weight acid, for example, an acid having a molecular weight of less than 210 g/mole. In some aspects, the organic acid has no more than nine carbon atoms, alternatively no more than six carbon atoms.
  • the organic acid in the detergent composition may have no more than four carbon atoms, or no more than three carbon atoms, or fewer than three carbon atoms. Specific examples of organic acids having fewer than three carbon atoms include formic acid and acetic acid.
  • compositions of the present disclosure comprise from about 5% to about 15%, or from about 6% to about 12%, or from about 6% to about 10%, or from about 7% to about 8.5%, by weight of the composition, of the organic acid.
  • Desirable viscosities in the present compositions are generally obtained through the careful selection of surfactants rather than through the addition of thickening agents.
  • the compositions described herein are substantially free of thickening agents.
  • the compositions comprise thickening agents to further build viscosity. Therefore, in some aspects, the composition comprises from about 0.01% to about 1%, or from about 0.02% to about 0.75%, or from about 0.05% to about 0.5%, by weight of the composition, of a thickening agent.
  • Thickening agents include methylcellulose, hydroxypropylmethylcellulose, xanthan gum, gellan gum, guar gum and hydroxypropyl guar gum, succinoglycan, and trihydroxystearin.
  • Other thickening agents include methylcellulose and hydroxypropylmethylcellulose thickeners available under the Methocel® trade name from Dow Chemical and Alcogum L520 from Akzo Nobel.
  • Thickening agent does not include detersive surfactants or their salts.
  • Thickening agents also includes certain salts, such as sodium chloride or sodium formate.
  • salts may be particularly undesirable, as salts may contribute to corrosion and stability issues.
  • the compositions of the present disclosure are substantially free of alkali metal halides, alkali earth metal halides, or mixtures thereof. In some aspects, no alkali metal halides or alkali earth metal halides are added to the compositions as free components.
  • the compositions are substantially free of sodium chloride and/or sodium formate. In some aspects, the compositions are substantially free of chloride ion and/or formate ion. In some aspects, the compositions are substantially free of formic acid.
  • the compositions may comprise less than about 0.5%, or less than about 0.1%, or less than about 0.01%, by weight of the composition, of sodium chloride, or of halide ions, or of chloride ions.
  • compositions described herein are low pH detergent compositions.
  • low pH it is meant that the compositions have a neat pH of less than about 7, or, in some aspects, of less than about 6.5.
  • the compositions have a neat pH of from about 1.5 to about 6.9, or from about 1.5 to about 6.5, or from about 1.5 to about 6, or from about 2 to about 5, or from about 2 to about 4, or from about 2 to about 3, or about 2.5.
  • a neutralizing (or alkalizing) agent is added to the composition in order to obtain the desired final neat pH of the composition.
  • Suitable neutralizing agents include alkaline metal, alkaline earth metal or substituted ammonium hydroxide, carbonate, bicarbonate, silicate, or mixtures thereof.
  • the neutralizing agent may be an amine or amide.
  • the neutralizing agent is an alkanolamine selected from monoethanolamine (MEA), diethanolamine, triethanolamine, 2-aminopropanol, monoisopropanol amine (MIPA), or mixtures thereof.
  • the alkalizing agent is NaOH, MEA, or mixtures thereof.
  • the composition comprises less than about 1%, or less than about 0.5%, or less than about 0.1%, by weight of the composition, alkanolamine. In some aspects, the composition comprises less than about 0.5% ethanolamine.
  • the detergent compositions of the present disclosure are capable of delivering a pH to the wash water (“wash water pH”), for example of a standard laundry bucket, of less than about 6.5, or less than about 6.2, or less than about 6.0.
  • the detergent compositions of the present invention are provided to the wash water in a sufficient amount such that the wash water contains from about 0.02% to about 4%, by weight of the wash water, of the detergent composition.
  • the wash water contains from about 0.03% to about 3%, by weight of the wash water, of the detergent, alternatively from about 0.04% to about 2% (about 400 to about 20,000 ppm).
  • reserve acidity refers to the grams of NaOH per 100 g of product required to attain a pH of 7.00.
  • the reserve acidity measurement as used herein is based upon titration (at standard temperature and pressure) of a 1% product solution in distilled water to an end point of pH 7.00, using standardized NaOH solution. Without being limited by theory, the reserve acidity measurement is found to be the best measure of the acidifying power of a composition, or the ability of a composition to provide a target acidic wash pH when added at high dilution into tap water, as opposed to pure or distilled water.
  • the reserve acidity is controlled by the level of formulated organic acid along with the neat product pH.
  • compositions described herein have a reserve acidity of at least about 1, or at least about 3, or at least about 5. In some aspects, the compositions herein have a reserve acidity to pH 7.00 of from about 3 to about 10, or from about 4 to about 7.
  • the compositions have viscosities greater than about 200 cps (centipoise) measured at 20 s ⁇ 1 at 21.1° C. In some aspects, the compositions have viscosities from about 200 cps to about 3000, or from about 200 to about 1500 cps, or from about 200 cps to about 1200 cps, or from about 200 cps to about 850 cps, or from about 250 cps to about 700 cps, or from about 200 cps to about 400 cps, measured at 20 s ⁇ 1 at 21.1° C.
  • Viscosities are measured at a shear rate of 20 s ⁇ 1 and at a temperature of 21.1° C. Viscosities can be measured with any suitable viscosity-measuring instrument, e.g., LVDVII+ or RVDVII+ Brookfield instruments.
  • compositions described herein are physically stable, meaning that the compositions do not significantly phase separate.
  • the composition is loaded into 10 mL vials and kept at 10° C., 25° C., and 40° C. for seven days. After seven days at each of the various temperatures, the vials are examined for phase separation.
  • a composition is determined to be phase stable at a particular temperature if (i) the composition remains free from splitting into two or more layers or (ii) it splits into layers but the major layer comprises at least 90% or at least 95% of the composition by weight.
  • compositions of the present invention may comprise one or more laundry adjuncts, such as dyes, bleaching agents, chelants, radical scavengers, perfumes, fluorescent whitening agents, suds supressors, soil suspension polymers, soil release polymers, dye-transfer inhibitors, fabric softening additives, structurant, builders, enzymes, preservatives, solvents, clay soil removal/anti-redeposition agents, and/or other benefit agents.
  • laundry adjuncts such as dyes, bleaching agents, chelants, radical scavengers, perfumes, fluorescent whitening agents, suds supressors, soil suspension polymers, soil release polymers, dye-transfer inhibitors, fabric softening additives, structurant, builders, enzymes, preservatives, solvents, clay soil removal/anti-redeposition agents, and/or other benefit agents.
  • the composition may comprise from about 0.01% to about 50% of an adjunct listed herein.
  • the composition may be substantially free of adjuncts. Suitable laundry adjuncts are further described, for example
  • compositions may comprise a dye to either provide a particular color to the composition itself (non-fabric substantive dyes) or to provide a hue to the fabric (hueing dyes).
  • the compositions of the present invention comprise from about 0.0001% to about 0.01%, by weight of the composition, of a non-fabric substantive dye and/or a hueing dye.
  • dyes useful herein include Basic Violet 3 (Cl 42555) and Basic Violet 4 (Cl 42600), both commercially available from Standard Dyes (High Point, N.C.), and Liquitint Violet 200 from Milliken Company.
  • compositions may comprise a bleaching agent.
  • the compositions of the present invention may contain from about 0.10% to about 10%, by weight of the composition, of a bleaching agent.
  • Bleaching agents useful herein include hydrogen peroxide or peroxyacids, such as 6-phthalimidoperoxyhexanoic acid.
  • the compositions may comprise a bleach activator, such as TAED or NOBS.
  • the bleaching agent may be in a different compartment than the surfactant.
  • the compositions are substantially free of bleaching agents.
  • compositions may comprise a chelant.
  • Chelants useful herein include DTPA, HEDP, DTPMP, polyfunctionally-substituted aromatic chelants (such as 1,2-dihydroxy-3,5-disulfobenzene (Tiron)), dipicolinic acid, and mixtures thereof.
  • compositions may comprise a radical scavenger which may be used with liquid hydrogen peroxide to provide stability.
  • Radical scavengers useful herein include trimethoxybenzoic acid.
  • compositions of the present invention may comprise perfume.
  • the perfume is typically an acid-stable perfume.
  • the compositions may comprise from about 0.1% to about 5%, or from about 0.5% to about 4%, or from about 1% to about 3%, or from about 2% to about 2.5%, by weight of the composition, of perfume.
  • compositions disclosed herein may comprise a perfume delivery system. Suitable perfume delivery systems, methods of making certain perfume delivery systems, and the uses of such perfume delivery systems are disclosed in USPA 2007/0275866 A1.
  • Such perfume delivery system may be a perfume microcapsule.
  • the perfume microcapsule may comprise a core that comprises perfume and a shell, with the shell encapsulating the core.
  • the shell may comprise a material selected from the group consisting of aminoplast copolymer, an acrylic, an acrylate, and mixtures thereof.
  • the aminoplast copolymer may be melamine-formaldehyde, urea-formaldehyde, cross-linked melamine formaldehyde, or mixtures thereof.
  • the perfume microcapsule's shell may be coated with one or more materials, such as a polymer, that aids in the deposition and/or retention of the perfume microcapsule on the site that is treated with the composition disclosed herein.
  • the polymer may be a cationic polymer selected from the group consisting of polysaccharides, cationically modified starch, cationically modified guar, polysiloxanes, poly diallyl dimethyl ammonium halides, copolymers of poly diallyl dimethyl ammonium chloride and vinyl pyrrolidone, acrylamides, imidazoles, imidazolinium halides, imidazolium halides, poly vinyl amine, copolymers of poly vinyl amine and N-vinyl formamide, and mixtures thereof.
  • the perfume microcapsule may be friable and/or have a mean particle size of from about 10 microns to about 500 microns or from about 20 microns to about 200 microns.
  • the composition comprises, based on total composition weight, from about 0.01% to about 80%, or from about 0.1% to about 50%, or from about 1.0% to about 25%, or from about 1.0% to about 10% of perfume microcapsules.
  • Suitable capsules may be obtained from Appleton Papers Inc., of Appleton, Wis. USA. Formaldehyde scavengers may also be used in or with such perfume microcapsules.
  • compositions may comprise a fluorescent whitening agent.
  • fluorescent whitening agents useful herein include those that are compatible with an acidic environment, such as Tinopal CBS-X.
  • compositions may comprise suds suppressor.
  • the compositions comprise from about 0.001% to about 0.02%, by weight of the composition, of suds suppressor.
  • suds suppressors useful herein include silica/silicone type, silicone oil, branched alcohols, or mixtures thereof.
  • compositions may comprise from about 0.001% to about 0.5% by weight of the composition of soil suspension polymers.
  • Soil suspension polymers include, without limitation, PEI ethoxylates, HMDA diquat ethoxylates, sulfonated derivatives, and hydrophobically modified anionic copolymers.
  • compositions may comprise from about 0.001% to about 0.5% by weight of the composition of soil release polymers.
  • Soil release polymers include, without limitation, a PET alkoxylate short block copolymer, an anionic derivative thereof, or mixtures thereof.
  • compositions may comprise dye transfer inhibitors and/or dye fixatives.
  • dye transfer inhibitors useful herein include polyvinylpyrrolidone, poly-4-vinylpyridine-N-oxide, copolymers of N-vinyl-2-pyrrolidone and N-vinylimidazole, or mixtures thereof.
  • Useful dye fixatives for this application are disclosed in U.S. Pat. No. 6,753,307.
  • compositions may comprise a fabric softening additive.
  • fabric softening additives useful herein include alkyl quaternary ammonium compounds, ester quaternary ammonium compounds, silicones, cationic silicones, or mixtures thereof.
  • compositions of the present invention typically rely on internal structuring rather than external structuring.
  • internal structuring it is meant that the detergent surfactants are relied on for structuring effect.
  • external structuring means structuring that relies on a nonsurfactant, e.g., crystallized glyceride(s), as structurants to achieve the desired rheology and particle suspending power.
  • compositions of the present invention are substantially free of external structuring systems.
  • the compositions are substantially free of hydroxyfunctional crystalline materials, including but not limited to hydrogenated castor oil (HCO).
  • HCO hydrogenated castor oil
  • the compositions comprise less than about 0.01%, or less than about 0.001%, by weight of the composition, of hydroxyfunctional crystalline materials, or of hydrogenated castor oil.
  • the compositions may comprise from about 0.01% to about 6%, by weight of the compositions, of hydroxyfunctional crystalline materials.
  • compositions may comprise from about 0.00001% to about 0.01% active enzymes that are stable and effective in a low-pH environment.
  • active enzymes include carbohydrase, amylase, cellulase, lipase, protease, or mixtures thereof.
  • the composition may comprise a builder.
  • Suitable builders herein can be selected from the group consisting of phosphates and polyphosphates, especially the sodium salts; aluminosilicates and silicates; carbonates, bicarbonates, sesquicarbonates and carbonate minerals other than sodium carbonate or sesquicarbonate; organic mono-, di-, tri-, and tetracarboxylates especially water-soluble nonsurfactant carboxylates in acid, sodium, potassium or alkanolammonium salt form, as well as oligomeric or water-soluble low molecular weight polymer carboxylates including aliphatic and aromatic types; and phytic acid.
  • borates e.g., for pH-buffering purposes
  • sulfates especially sodium sulfate and any other fillers or carriers which may be important to the engineering of stable surfactant and/or builder-containing detergent compositions.
  • compositions may comprise a preservative. Suitable preservatives may be selected by one of ordinary skill in the art and may include ProxelTM (available from Arch Chemicals/Lonza).
  • the composition may comprise from about 0.01% to about 2.0%, or about 0.1% to about 1.0%, or about 0.1% to about 0.3%, by weight of the composition, of preservative. In some aspects, the compositions comprise less than 0.01% of a preservative. In some aspects, the compositions are substantially free of preservatives.
  • the composition comprises water and is substantially free of organic solvent.
  • the composition may comprise organic solvent.
  • Preferred organic solvents include 1,2-propanediol, ethanol, glycerol, dipropylene glycol, methyl propane diol and mixtures thereof.
  • compositions comprise from about 0.05% to about 25%, or from about 0.1% to about 15%, or from about 1% to about 10%, or from about 2% to about 5%, by weight of the composition, organic solvent. In some aspects, the composition comprises less than 5% or less than 1% of organic solvent.
  • compositions may comprise clay soil removal/anti-redeposition agents, such as water-soluble ethoxylated amines.
  • clay soil removal/anti-redeposition agents such as water-soluble ethoxylated amines.
  • Other exemplary clay soil removal and anti-redeposition agents are described in U.S. Pat. Nos. 4,597,898; 548,744; 4,891,160; European Patent Application Nos. 111,965; 111,984; 112,592; and WO 95/32272.
  • the concentrated compositions comprise about 0.005% to about 5% by weight of clay soil removal/anti-redeposition agents.
  • the composition is substantially free of clay soil removal/anti-redeposition agents.
  • the present disclosure provides a method for treating a surface, for example, fabric, with the compositions disclosed herein.
  • the method comprises the steps of optionally washing and/or rinsing the surface, contacting the surface with the disclosed composition, then optionally washing and/or rinsing the surface.
  • the surface may optionally be dried.
  • the surface may be contacted with the composition in neat form or in dilute form; in some aspects, the composition may be mixed with wash water.
  • the method for treating a surface may be performed manually, such as by hand washing, or in an automated fashion, such as by a machine, e.g., a laundry washing machine.
  • compositions according to the present disclosure are shown below in Tables 2, 3, and 4.
  • compositions To prepare the compositions, add about 80% of the composition's water to a batch tank. Add about 80% of the composition's base (e.g., NaOH or MEA). Gently agitate. While mixing, add the acid, then the surfactants. Continue agitating until the surfactants are completely blended; while blending, the agitation may be increased. Once the surfactants are completely blended, the other adjuncts may be added (polymers, chelants, dyes, perfumes, etc.). Titrate to the desired final neat pH by adding parts of the remaining base. Balance with the remaining water.
  • base e.g., NaOH or MEA
  • the pH of the compositions is measured using a sympHony SP70P pH meter (VWR of Radnor, Pa.).
  • Examples 1-8 in Table 2 are formulations according to the present invention.
  • Example 17 is a comparative example comprising two nonionic surfactants that are not selected in accordance with the present invention (e.g., both nonionic surfactants have HLB values above 10).
  • the viscosity of Example 17 is less than the viscosities of compositions according to the present invention.
  • Examples 18-20 in Table 4 are comparative examples.

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